Hard mask composition, hard mask layer and method for forming pattern

Abstract

The present invention provides a hard mask composition, a hard mask layer, and a method for forming a pattern, wherein the hard mask composition comprises a polymer and a solvent, wherein the polymer comprises a structural unit represented by Chemical Formula 1. In Chemical Formula 1, the definitions of A, B, and R1 to R5 are as described in the present specification. The hard mask composition can improve etching resistance and film density. [Chemical Formula 1] #imgabs0#

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to and the benefit of Korean Patent Application No. 10-2019-0127125 filed in the Korean Intellectual Property Office on October 14, 2019, the entire contents of which are incorporated herein by reference. Technical Field

[0003] Disclosed are a hard mask composition, a hard mask layer comprising a cured product of the hard mask composition, and a method of forming a pattern using the hard mask composition. Background Art

[0004] Recently, the semiconductor industry has developed into ultra-fine technology with patterns of a few nanometers to tens of nanometers in size. Such ultra-fine technology mainly requires efficient photolithography technology.

[0005] A typical photolithography technique includes: providing a material layer on a semiconductor substrate; coating a photoresist layer on the material layer; exposing and developing the photoresist layer to provide a photoresist pattern; and etching the material layer using the photoresist pattern as a mask.

[0006] Nowadays, it is difficult to provide a fine pattern with an excellent profile only by the above-mentioned typical photolithography technology according to the small size of the pattern to be formed. Therefore, an auxiliary layer called a hard mask layer may be formed between the material layer and the photoresist layer to provide a fine pattern. Summary of the invention

[0007] Embodiments provide a hard mask composition capable of improving etching resistance.

[0008] Another embodiment provides a hard mask layer including a cured product of the hard mask composition.

[0009] Another embodiment provides a method of forming a pattern using the hard mask composition.

[0010] According to an embodiment, a hard mask composition including a polymer including a structural unit represented by Chemical Formula 1 and a solvent is provided.

[0011] [Chemical formula 1]

[0012]

[0013] In Chemical Formula 1,

[0014] A is a substituted or unsubstituted pyrenylene group,

[0015] B is hydrogen, deuterium, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, halogen, nitro, amino, hydroxyl, or a combination thereof,

[0016] R 1 to R 5 are independently hydrogen, deuterium, hydroxyl, substituted or unsubstituted C1 to C30 alkoxy, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C2 to C30 alkenyl, substituted or unsubstituted C2 to C30 alkynyl, substituted or unsubstituted C1 to C30 heteroalkyl, substituted or unsubstituted C3 to C30 cycloalkyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C3 to C30 heterocyclyl, or a combination thereof, and

[0017] R 1 to R 5 At least two of the groups are independently hydroxy, substituted or unsubstituted C1 to C30 alkoxy, or a combination thereof.

[0018] A may be an unsubstituted pyrene group or a pyrene group substituted by at least one substituent, wherein the substituents may independently be deuterium, hydroxyl, substituted or unsubstituted C1 to C30 alkoxy, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C2 to C30 alkenyl, substituted or unsubstituted C2 to C30 alkynyl, substituted or unsubstituted C1 to C30 heteroalkyl, substituted or unsubstituted C3 to C30 cycloalkyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C3 to C30 heterocyclyl, or a combination thereof.

[0019] A may be an unsubstituted pyrene group or a pyrene group substituted with at least one hydroxyl group.

[0020] R 1 to R 5 Two or three of the groups may independently be hydroxy, substituted or unsubstituted methoxy, substituted or unsubstituted ethoxy, substituted or unsubstituted propoxy, substituted or unsubstituted butoxy, or a combination thereof.

[0021] R 3 and R 4 may independently be hydroxy, substituted or unsubstituted methoxy, substituted or unsubstituted ethoxy, substituted or unsubstituted propoxy, substituted or unsubstituted butoxy, or a combination thereof;

[0022] R 3 and R 5may independently be hydroxy, substituted or unsubstituted methoxy, substituted or unsubstituted ethoxy, substituted or unsubstituted propoxy, substituted or unsubstituted butoxy, or a combination thereof; or

[0023] R 1 , R 3 and R 5 The radicals may independently be hydroxy, substituted or unsubstituted methoxy, substituted or unsubstituted ethoxy, substituted or unsubstituted propoxy, substituted or unsubstituted butoxy, or a combination thereof.

[0024] The structural unit represented by Chemical Formula 1 may be represented by one of Chemical Formulas 2 to 4.

[0025] [Chemical formula 2]

[0026]

[0027] [Chemical formula 3]

[0028]

[0029] [Chemical formula 4]

[0030]

[0031] In Chemical Formula 2 to Chemical Formula 4,

[0032] B is hydrogen, deuterium, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, halogen, nitro, amino, hydroxyl, or a combination thereof,

[0033] R 1 , R 3 , R 4 and R 5 are independently hydroxy, substituted or unsubstituted methoxy, substituted or unsubstituted ethoxy, substituted or unsubstituted propoxy, substituted or unsubstituted butoxy, or a combination thereof, and

[0034] R 6 is hydrogen, hydroxy, substituted or unsubstituted methoxy, substituted or unsubstituted ethoxy, substituted or unsubstituted propoxy, substituted or unsubstituted butoxy, or a combination thereof.

[0035] The structural unit represented by Chemical Formula 1 may be derived from the following reaction mixture: substituted or unsubstituted pyrene, and

[0036] Benzaldehyde substituted with at least two substituents, wherein the substituents may independently be hydroxyl, substituted or unsubstituted C1 to C30 alkoxy, or a combination thereof.

[0037] The substituted or unsubstituted pyrene may be pyrene or hydroxypyrene.

[0038] The benzaldehyde substituted with at least two substituents is dihydroxybenzaldehyde, hydroxymethoxybenzaldehyde, hydroxyethoxybenzaldehyde, hydroxypropoxybenzaldehyde, hydroxybutoxybenzaldehyde, trihydroxybenzaldehyde or a combination thereof.

[0039] According to another embodiment, a hard mask layer including a cured product of a hard mask composition is provided.

[0040] According to another embodiment, a method of forming a pattern includes: coating a hard mask composition on a material layer and heat treating the resultant to form a hard mask layer, forming a photoresist layer on the hard mask layer, exposing and developing the photoresist layer to form a photoresist pattern, selectively removing the hard mask layer using the photoresist pattern to expose a portion of the material layer, and etching the exposed portion of the material layer.

[0041] The solubility of the polymer and the etching resistance and film density of the hard mask layer can be ensured at the same time. DETAILED DESCRIPTION

[0042] Hereinafter, example embodiments of the present disclosure will be described in detail and can be easily performed by those skilled in the art. However, the present disclosure can be implemented in many different ways and should not be construed as being limited to the example embodiments set forth herein.

[0043] As used herein, when a definition is not otherwise provided, "substituted" refers to replacement of a hydrogen atom of a compound by a substituent selected from the group consisting of deuterium, a halogen atom (F, Br, Cl or I), a hydroxyl group, a nitro group, a cyano group, an amino group, an azido group, an amidino group, a hydrazino group, a hydrazono group, a carbonyl group, a carbamoyl group, a thiol group, an ester group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphate group or a salt thereof, a C1 to C30 alkyl group, a C2 to C30 alkenyl group, a C2 to C30 alkynyl group, a C6 to C30 aryl group, a C7 to C30 aralkyl group, a C1 to C30 alkoxy group, a C1 to C30 heteroalkyl group, a C3 to C30 heteroarylalkyl group, a C3 to C30 cycloalkyl group, a C3 to C15 cycloalkenyl group, a C6 to C15 cycloalkynyl group, a C2 to C30 heterocyclyl group, and combinations thereof.

[0044] In addition, two adjacent substituents of a substituted halogen atom (F, Br, Cl or I), a hydroxyl group, a nitro group, a cyano group, an amino group, an azido group, an amidino group, a hydrazine group, a hydrazone group, a carbonyl group, a carbamoyl group, a thiol group, an ester group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphate group or a salt thereof, a C1 to C30 alkyl group, a C2 to C30 alkenyl group, a C2 to C30 alkynyl group, a C6 to C30 aryl group, a C7 to C30 aralkyl group, a C1 to C30 alkoxy group, a C1 to C30 heteroalkyl group, a C3 to C30 heteroarylalkyl group, a C3 to C30 cycloalkyl group, a C3 to C15 cycloalkenyl group, a C6 to C15 cycloalkynyl group, and a C2 to C30 heterocyclyl group may be fused to form a ring. For example, a substituted C6 to C30 aryl group may be fused with another adjacent substituted C6 to C30 aryl group to form a substituted or unsubstituted fluorene ring.

[0045] As used herein, when a definition is not otherwise provided, “hetero” refers to a group including 1 to 3 heteroatoms selected from N, O, S, Se and P.

[0046] As used herein, "aryl" refers to a group comprising at least one hydrocarbon aromatic moiety, and comprises a hydrocarbon aromatic moiety linked by a single bond and a hydrocarbon aromatic moiety fused directly or indirectly to provide a non-aromatic fused ring. The aryl group may comprise a monocyclic, polycyclic or fused polycyclic (i.e., rings that share adjacent pairs of carbon atoms) functional groups.

[0047] As used herein, "heterocyclic group" is a concept including heteroaryl groups, and may contain at least one heteroatom selected from N, O, S, P and Si, rather than carbon (C) in a cyclic compound (such as an aryl group, a cycloalkyl group, a condensed ring thereof or a combination thereof). When the heterocyclic group is a condensed ring, all or each ring of the heterocyclic group may contain one or more heteroatoms.

[0048] More specifically, the substituted or unsubstituted aryl group may be a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted phenanthryl group, a substituted or unsubstituted naphthacenyl group, a substituted or unsubstituted pyrenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted quaterphenyl group, a substituted or unsubstituted chrysenyl group, a substituted or unsubstituted triphenylene group, a substituted or unsubstituted perylenyl group, a substituted or unsubstituted indenyl group, a substituted or unsubstituted fluorenyl group, a combination thereof, or a combined condensed ring of the foregoing groups, but is not limited thereto.

[0049] More specifically, the substituted or unsubstituted heterocyclic group may be a substituted or unsubstituted furanyl group, a substituted or unsubstituted thiophenyl group, a substituted or unsubstituted pyrrolyl group, a substituted or unsubstituted pyrazolyl group, a substituted or unsubstituted imidazolyl group, a substituted or unsubstituted triazolyl group, a substituted or unsubstituted oxazolyl group, a substituted or unsubstituted thiazolyl group, a substituted or unsubstituted oxadiazolyl group, a substituted or unsubstituted thiadiazolyl group, a substituted or unsubstituted pyridinyl group, a substituted or unsubstituted pyrimidinyl group, a substituted or unsubstituted pyrazinyl group, a substituted or unsubstituted triazinyl group, or a substituted or unsubstituted thiazolyl group. group), substituted or unsubstituted benzofuranyl, substituted or unsubstituted benzothiophenyl, substituted or unsubstituted benzimidazolyl, substituted or unsubstituted indolyl, substituted or unsubstituted quinolinyl, substituted or unsubstituted isoquinolinyl, substituted or unsubstituted quinazolinyl, substituted or unsubstituted quinoxalinyl, substituted or unsubstituted naphthyridinyl, substituted or unsubstituted benzoxazinyl, substituted or unsubstituted benzthiazinyl, substituted or unsubstituted acridinyl, substituted or unsubstituted phenazinyl, substituted or unsubstituted phenothiazinyl, substituted or unsubstituted phenoxazinyl group), substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiphenyl group, substituted or unsubstituted carbazolylgroup), substituted or unsubstituted pyridoindolyl group, substituted or unsubstituted benzopyridooxazinyl group, substituted or unsubstituted benzopyridothiazinyl group, substituted or unsubstituted 9,9-dimethyl 9,10 dihydroacridinyl group, a combination thereof or a fused ring of the aforementioned groups, but not limited thereto. In one example of the present invention, the heterocyclic group or heteroaryl group may be a pyrrolyl group, an indolyl group or a carbazolyl group.

[0050] As used herein, polymer is meant to encompass both oligomers and polymers.

[0051] Hereinafter, a hard mask composition according to an embodiment is described.

[0052] A hard mask composition according to an embodiment includes a polymer and a solvent.

[0053] The polymer may include a main chain including an aromatic ring and a side chain including an aromatic ring bonded to the main chain and substituted with at least two substituents.

[0054] The main chain containing an aromatic ring may contain a condensed aromatic ring and may contain, for example, substituted or unsubstituted pyrene. The side chain containing an aromatic ring substituted with at least two substituents may contain benzene substituted with at least two substituents. Herein, the substituent may be a hydrophilic functional group, for example, a hydroxyl group, a substituted or unsubstituted alkoxy group.

[0055] Therefore, by including an aromatic ring having a high carbon content in the main chain, a hard film-type polymer layer can be formed, thereby improving etching resistance, and by including an aromatic ring having a hydrophilic functional group in the side chain, solubility to a solvent can be improved.

[0056] For example, the polymer may include a structural unit represented by Chemical Formula 1.

[0057] [Chemical formula 1]

[0058]

[0059] In Chemical Formula 1,

[0060] A is a substituted or unsubstituted pyrene group,

[0061] B is hydrogen, deuterium, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, halogen, nitro, amino, hydroxyl, or a combination thereof,

[0062] R 1 to R 5 are the same or different and are independently hydrogen, deuterium, hydroxyl, substituted or unsubstituted C1 to C30 alkoxy, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C2 to C30 alkenyl, substituted or unsubstituted C2 to C30 alkynyl, substituted or unsubstituted C1 to C30 heteroalkyl, substituted or unsubstituted C3 to C30 cycloalkyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C3 to C30 heterocyclyl, or a combination thereof, and

[0063] R 1 to R 5 At least two of the groups are independently hydroxy, substituted or unsubstituted C1 to C30 alkoxy, or a combination thereof.

[0064] For example, A may be an unsubstituted pyrene or a pyrene substituted by at least one substituent which is the same or different, wherein the substituents may independently be deuterium, hydroxyl, substituted or unsubstituted C1 to C30 alkoxy, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C2 to C30 alkenyl, substituted or unsubstituted C2 to C30 alkynyl, substituted or unsubstituted C1 to C30 heteroalkyl, substituted or unsubstituted C3 to C30 cycloalkyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C3 to C30 heterocyclyl, or a combination thereof.

[0065] For example, in A, when the number of substituents is plural, all substituents may be substituted with the same ring among the rings in pyrene, or may be substituted with different rings among the rings in pyrene.

[0066] For example, A can be an unsubstituted pyrene group, a pyrene group substituted with one substituent, or a pyrene group substituted with two substituents.

[0067] For example, A may be an unsubstituted pyrenylene, a pyrenylene substituted by at least one hydroxyl group, or a pyrenylene substituted by at least one C1 to C30 alkoxy group. Herein, the C1 to C30 alkoxy group may be a substituted or unsubstituted methoxy group, a substituted or unsubstituted ethoxy group, a substituted or unsubstituted propoxy group, a substituted or unsubstituted butoxy group, or a combination thereof.

[0068] For example, A may be an unsubstituted pyrene group, a pyrene group substituted with one or two hydroxyl groups, and for example, A may be a pyrene group, a 1-hydroxypyrene group, or a 2-hydroxypyrene group, but is not limited thereto.

[0069] As described above, the polymer may include benzene substituted by at least two hydrophilic functional groups in the side chain, and the benzene substituted by at least two hydrophilic functional groups in the side chain and the substituted or unsubstituted pyrene group in the main chain may be bonded to a tertiary carbon or a quaternary carbon. Therefore, the polymer may have increased solubility to a solvent and may be effectively applied to a solution method such as spin coating, and may have increased solubility to N 2 / O 2 The mixed gas improves etching resistance and provides a polymer layer with improved film density.

[0070] For example, R 1 to R 5 may be the same or different and may independently be hydrogen, deuterium, hydroxyl, substituted or unsubstituted C1 to C30 alkoxy, or a combination thereof. Specifically, R 1 to R 5 may be the same or different and may independently be hydrogen, deuterium, hydroxyl, substituted or unsubstituted methoxy, substituted or unsubstituted ethoxy, substituted or unsubstituted propoxy, substituted or unsubstituted butoxy, or a combination thereof.

[0071] For example, R 1 to R 5 2 to 5 of them may independently be hydroxyl, substituted or unsubstituted C1 to C30 alkoxy, or a combination thereof, and for example, R 1 to R 5 Two or three of them may independently be hydroxyl, substituted or unsubstituted C1 to C30 alkoxy, or a combination thereof.

[0072] For example, R 3 It may be a hydroxy group, a substituted or unsubstituted C1 to C30 alkoxy group, or a combination thereof, and is desirably a hydroxy group.

[0073] For example, R 3 and R 4 may be the same or different and may independently be hydroxy, substituted or unsubstituted C1 to C30 alkoxy, or a combination thereof;

[0074] R 3 and R 5 may be the same or different and may independently be hydroxy, substituted or unsubstituted C1 to C30 alkoxy, or a combination thereof; or

[0075] R 1 , R 3 and R 5 The groups may be the same or different and may independently be hydroxy, substituted or unsubstituted C1 to C30 alkoxy, or a combination thereof.

[0076] For example, R 3 It can be hydroxyl, R4 It can be hydroxy or substituted or unsubstituted C1 to C30 alkoxy; R 3 and R 5 It can be hydroxyl; or R 1 , R 3 and R 5 It may be a hydroxyl group.

[0077] For example, R 1 to R 5 At least two of the may independently be hydroxy, substituted or unsubstituted methoxy, substituted or unsubstituted ethoxy, substituted or unsubstituted propoxy, substituted or unsubstituted butoxy, or a combination thereof.

[0078] For example, R 1 to R 5 Two to five of them may independently be hydroxyl, substituted or unsubstituted methoxy, substituted or unsubstituted ethoxy, substituted or unsubstituted propoxy, substituted or unsubstituted butoxy or a combination thereof. For example, R 1 to R 5 Two or three of them may independently be hydroxy, substituted or unsubstituted methoxy, substituted or unsubstituted ethoxy, substituted or unsubstituted propoxy, substituted or unsubstituted butoxy, or a combination thereof.

[0079] For example, R 3 It may be a hydroxyl group, a substituted or unsubstituted methoxy group, a substituted or unsubstituted ethoxy group, a substituted or unsubstituted propoxy group, a substituted or unsubstituted butoxy group, or a combination thereof, and is desirably a hydroxyl group.

[0080] For example, R 3 and R 4 may be the same or different and may independently be hydroxy, substituted or unsubstituted methoxy, substituted or unsubstituted ethoxy, substituted or unsubstituted propoxy, substituted or unsubstituted butoxy, or a combination thereof;

[0081] R 3 and R 5 may be the same or different and may independently be hydroxy, substituted or unsubstituted methoxy, substituted or unsubstituted ethoxy, substituted or unsubstituted propoxy, substituted or unsubstituted butoxy, or a combination thereof; or

[0082] R 1 , R 3 and R 5The groups may be the same or different and may independently be hydroxy, substituted or unsubstituted methoxy, substituted or unsubstituted ethoxy, substituted or unsubstituted propoxy, substituted or unsubstituted butoxy, or a combination thereof.

[0083] For example, R 3 It can be hydroxyl, R 4 R may be hydroxy, substituted or unsubstituted methoxy, substituted or unsubstituted ethoxy, substituted or unsubstituted propoxy or substituted or unsubstituted butoxy; 3 and R 5 It can be hydroxyl; or R 1 , R 3 and R 5 It may be a hydroxyl group.

[0084] For example, R 2 It may be hydrogen.

[0085] The structural unit represented by Chemical Formula 1 may be represented by one of Chemical Formulas 2 to 4.

[0086] [Chemical formula 2]

[0087]

[0088] [Chemical formula 3]

[0089]

[0090] [Chemical formula 4]

[0091]

[0092] In Chemical Formula 2 to Chemical Formula 4,

[0093] B.R 1 , R 3 , R 4 and R 5 Same as above, and

[0094] R 6 is hydrogen, hydroxy, substituted or unsubstituted C1 to C30 alkoxy, or a combination thereof.

[0095] For example, R 6 It may be hydrogen, hydroxy, substituted or unsubstituted methoxy, substituted or unsubstituted ethoxy, substituted or unsubstituted propoxy, substituted or unsubstituted butoxy, or a combination thereof.

[0096] For example, the structural unit represented by Chemical Formula 1 may be derived from a reaction mixture comprising substituted or unsubstituted pyrene and benzaldehyde substituted by at least two substituents. Herein, the substituents may be independently deuterium, hydroxyl, substituted or unsubstituted C1 to C30 alkoxy, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C2 to C30 alkenyl, substituted or unsubstituted C2 to C30 alkynyl, substituted or unsubstituted C1 to C30 heteroalkyl, substituted or unsubstituted C3 to C30 cycloalkyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C3 to C30 heterocyclyl, or a combination thereof, and desirably independently hydroxyl, substituted or unsubstituted C1 to C30 alkoxy, or a combination thereof.

[0097] The structural unit may be obtained by a condensation reaction of a reaction mixture, but is not limited thereto.

[0098] For example, the substituted or unsubstituted pyrene may be unsubstituted pyrene or pyrene substituted with at least one substituent which is the same as or different from each other. Herein, when the number of substituents is plural, all substituents may be substituted with the same ring among the rings in pyrene, or may be substituted with different rings among the rings in pyrene.

[0099] For example, the substituted or unsubstituted pyrene may be unsubstituted pyrene, pyrene substituted with one substituent, or pyrene substituted with two substituents.

[0100] For example, the substituted or unsubstituted pyrene may be unsubstituted pyrene, pyrene substituted by at least one hydroxyl group, pyrene substituted by at least one C1 to C30 alkoxy group, or a combination thereof. Herein, the C1 to C30 alkoxy group may be a substituted or unsubstituted methoxy group, a substituted or unsubstituted ethoxy group, a substituted or unsubstituted propoxy group, a substituted or unsubstituted butoxy group, or a combination thereof.

[0101] For example, the substituted or unsubstituted pyrene may be pyrene or pyrene substituted with one or two hydroxyl groups, such as pyrene, 1-hydroxypyrene, or 2-hydroxypyrene, but is not limited thereto.

[0102] For example, the benzaldehyde substituted with at least two substituents may be benzaldehyde substituted with 2 to 5 substituents which are the same as or different from each other, for example, benzaldehyde substituted with 2 or 3 substituents.

[0103] For example, the benzaldehyde substituted by at least two substituents may be benzaldehyde substituted by at least two hydroxyl groups, benzaldehyde substituted by at least two C1 to C30 alkoxy groups, and benzaldehyde substituted by at least one hydroxyl group and at least one C1 to C30 alkoxy group, or a combination thereof. For example, the benzaldehyde substituted by at least two substituents may be benzaldehyde substituted by two hydroxyl groups, benzaldehyde substituted by three hydroxyl groups, benzaldehyde substituted by two C1 to C30 alkoxy groups, benzaldehyde substituted by three C1 to C30 alkoxy groups, benzaldehyde substituted by one hydroxyl group and one C1 to C30 alkoxy group, or a combination thereof. Herein, the C1 to C30 alkoxy group may be a substituted or unsubstituted methoxy group, a substituted or unsubstituted ethoxy group, a substituted or unsubstituted propoxy group, a substituted or unsubstituted butoxy group, or a combination thereof.

[0104] For example, the benzaldehyde substituted with at least two substituents may be dihydroxybenzaldehyde, hydroxymethoxybenzaldehyde, hydroxyethoxybenzaldehyde, hydroxypropoxybenzaldehyde, hydroxybutoxybenzaldehyde, trihydroxybenzaldehyde, or a combination thereof.

[0105] For example, the benzaldehyde substituted with at least two substituents may be 3,4-dihydroxybenzaldehyde, 2,4-dihydroxybenzaldehyde, 4-hydroxy-3-methoxybenzaldehyde, or 2,4,6-trihydroxybenzaldehyde, but is not limited thereto.

[0106] The polymer may include one or more structural units represented by Chemical Formula 1, and the plurality of structural units represented by Chemical Formula 1 may be the same as or different from each other.

[0107] The polymer may include the structural unit represented by Chemical Formula 1 as a plurality of repeating units, and the number and arrangement of the repeating units are not limited.

[0108] The polymer may further include one or more other structural units in addition to the structural units described above, and the number and arrangement of the structural units are not limited.

[0109] The polymer may have a weight average molecular weight of about 500 to about 200,000. More specifically, the polymer may have a weight average molecular weight of about 1,000 to about 100,000, about 1,200 to about 50,000, or about 1,500 to about 10,000. When the polymer has a weight average molecular weight within the range, the polymer can be optimized by adjusting the carbon amount and solubility in the solvent.

[0110] On the other hand, the solvent used in the hard mask composition may be any one that is sufficiently soluble or dispersible for the polymer, and may include, for example, at least one selected from the following: propylene glycol, propylene glycol diacetate, methoxypropylene glycol, diethylene glycol, diethylene glycol butyl ether, tri(ethylene glycol) monomethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, ethyl lactate, γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, methylpyrrolidone, methylpyrrolidinone, acetylacetone and ethyl 3-ethoxypropionate, but is not limited thereto.

[0111] The polymer may be included in an amount of about 0.1 wt % to about 50 wt %, about 0.5 wt % to about 40 wt %, about 1 wt % to about 30 wt %, or about 3 wt % to about 20 wt % based on the total amount of the hard mask composition. When the polymer is included within the range, the thickness, surface roughness, and planarization of the hard mask may be controlled.

[0112] The hardmask composition may further include additives of surfactants, crosslinking agents, thermal acid generators, or plasticizers.

[0113] The surfactant may include, for example, fluoroalkyl compounds, alkylbenzene sulfonates, alkylpyridinium salts, polyethylene glycol, or quaternary ammonium salts, but is not limited thereto.

[0114] The crosslinking agent may be, for example, a melamine-based, substituted urea-based or polymer-based crosslinking agent. Desirably, it may be a crosslinking agent having at least two crosslink-forming substituents, for example, a compound such as methoxymethylated glycoluril, butoxymethylated glycoluril, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguanamine, butoxymethylated benzoguanamine, methoxymethylated urea, butoxymethylated urea, methoxymethylated thiourea or butoxymethylated thiourea and the like.

[0115] The crosslinking agent may be a crosslinking agent having high heat resistance. The crosslinking agent having high heat resistance may be a compound including a crosslinking substituent including an aromatic ring (eg, a benzene ring or a naphthalene ring) in a molecule.

[0116] The thermal acid generator may be, for example, an acidic compound such as p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium p-toluenesulfonic acid, salicylic acid, sulfosalicylic acid, citric acid, benzoic acid, hydroxybenzoic acid, naphthalenecarbonic acid and the like, or / and 2,4,4,6-tetrabromocyclohexadienonone, benzoin toluenesulfonate, 2-nitrobenzyl toluenesulfonate, other organic alkyl sulfonates and the like, but is not limited thereto.

[0117] The additive may be included in an amount of about 0.001 to 40 parts by weight, about 0.01 to 30 parts by weight, or about 0.1 to 20 parts by weight based on 100 parts by weight of the hardmask composition. Within the range, solubility may be improved without changing optical properties of the hardmask composition.

[0118] According to another embodiment, an organic layer produced using a hard mask composition is provided. The organic layer may be formed, for example, by coating the hard mask composition on a substrate and heat treating it to cure, and may include, for example, a hard mask layer for electronic devices, a planarization layer, a sacrificial layer, a filler, and the like.

[0119] According to another embodiment, a hard mask layer including a cured product of the aforementioned hard mask composition is provided.

[0120] For example, the cured product includes condensed polycyclic aromatic hydrocarbons.

[0121] Since the cured product includes the condensed polycyclic aromatic hydrocarbons, it may exhibit high etching resistance that can withstand etching gas and chemical liquid exposed in subsequent processes including an etching process.

[0122] Hereinafter, a method of forming a pattern using the aforementioned hard mask composition is described.

[0123] The method of forming a pattern according to an embodiment includes: forming a material layer on a substrate, coating a hard mask composition including the aforementioned polymer and a solvent on the material layer, thermally treating the hard mask composition to form a hard mask layer, forming a photoresist layer on the hard mask layer, exposing and developing the photoresist layer to form a photoresist pattern, selectively removing the hard mask layer using the photoresist pattern to expose a portion of the material layer, and etching the exposed portion of the material layer.

[0124] The substrate may be, for example, a silicon wafer, a glass substrate or a polymer substrate.

[0125] The material layer is a material that will eventually be patterned, for example, a metal layer such as an aluminum layer and a copper layer; a semiconductor layer such as a silicon layer; or an insulating layer such as a silicon oxide layer and a silicon nitride layer. The material layer can be formed by a method such as a chemical vapor deposition (CVD) process.

[0126] The hard mask composition is the same as described above, and may be applied in the form of a solution by a spin coating method. Herein, the thickness of the hard mask composition is not particularly limited, but may be, for example, about 50 angstroms to about 200,000 angstroms.

[0127] The heat treatment of the hard mask composition may be performed, for example, at about 100° C. to about 700° C. for about 10 seconds to about 1 hour.

[0128] For example, the method may further include forming a silicon-containing thin layer on the hard mask layer. The silicon-containing thin layer may be formed of materials such as SiCN, SiOC, SiON, SiOCN, SiC, SiO, and / or SiN, and the like.

[0129] For example, the method may further include forming a bottom antireflective coating (BARC) on an upper surface of the silicon-containing thin layer or on an upper surface of the hard mask layer before forming the photoresist layer.

[0130] The exposure of the photoresist layer may be performed using, for example, ArF, KrF, or EUV. After the exposure, a heat treatment may be performed at about 100° C. to about 700° C.

[0131] The etching process of the exposed portion of the material layer may be performed by a dry etching process using an etching gas, and the etching gas may be, for example, N 2 / O 2 , CHF 3 CF 4 , Cl 2 , BCl 3 and their mixed gases.

[0132] The etched material layer may be formed in a plurality of patterns, and the plurality of patterns may be metal patterns, semiconductor patterns, insulating patterns, and the like, such as different patterns of semiconductor integrated circuit devices.

[0133] Hereinafter, the embodiments are described in more detail with reference to examples. However, these examples are exemplary, and the present scope is not limited thereto.

[0134] Polymer synthesis

[0135] Synthesis Example 1

[0136] 1-Hydroxypyrene (21.8 g, 0.1 mol) and 3,4-dihydroxybenzaldehyde (13.8 g, 0.1 mol) were added to a 250 ml flask, and then, a solution prepared by dissolving p-toluenesulfonic acid monohydrate (0.57 g, 0.03 mmol) in 100 g of propylene glycol monomethyl ether acetate (PGMEA) was added thereto. The obtained mixture was stirred at 90°C to perform a polymerization reaction, and the reaction was completed when the weight average molecular weight reached 2,000 to 2,500. When the polymerization reaction was completed, the reactant was cooled to room temperature, and then, 300 g of distilled water and 300 g of methanol were added thereto, and then, it was stirred vigorously and allowed to stand. After removing the supernatant therefrom, the precipitate therein was dissolved in 100 g of PGMEA, 300 g of methanol and 300 g of distilled water were added thereto, and then, it was stirred vigorously and allowed to stand (primary process). After removing the supernatant again, the precipitate therein was dissolved in 80 g of PGMEA (secondary process). One primary process and one secondary process were regarded as one purification process, which was performed three times in total. After the three purification processes, the polymer obtained therefrom was dissolved in 80 g of PGMEA, concentrated under reduced pressure to remove residual methanol and distilled water, and a polymer containing a structural unit (repeating unit) represented by Chemical Formula 1a was obtained. (Mw: 2,455)

[0137] [Chemical formula 1a]

[0138]

[0139] Synthesis Example 2

[0140] A polymer including a structural unit (repeating unit) represented by Chemical Formula 1b was synthesized according to the same method as Synthesis Example 1 except that 4-hydroxy-3-methoxybenzaldehyde (15.2 g, 0.1 mol) was used instead of 3,4-dihydroxybenzaldehyde (13.8 g, 0.1 mol). (Mw: 2,785)

[0141] [Chemical formula 1b]

[0142]

[0143] Synthesis Example 3

[0144] A polymer including a structural unit (repeating unit) represented by Chemical Formula 1c was synthesized according to the same method as Synthesis Example 1 except that 2,4,6-trihydroxybenzaldehyde (15.4 g, 0.1 mol) was used instead of 3,4-dihydroxybenzaldehyde (13.8 g, 0.1 mol). (Mw: 2,127)

[0145] [Chemical formula 1c]

[0146]

[0147] Synthesis Example 4

[0148] A polymer including a structural unit (repeating unit) represented by Chemical Formula 1d was synthesized according to the same method as Synthesis Example 1, except that pyrene (20.2 g, 0.1 mol) was used instead of 1-hydroxypyrene (21.8 g, 0.1 mol) and 2,4-dihydroxybenzaldehyde (13.8 g, 0.1 mol) was used instead of 3,4-dihydroxybenzaldehyde (13.8 g, 0.1 mol). (Mw: 2,086)

[0149] [Chemical formula 1d]

[0150]

[0151] Synthesis Comparative Example 1

[0152] A polymer including a structural unit (repeating unit) represented by Chemical Formula A was synthesized according to the same method as Synthesis Example 1 except that 4-hydroxybenzaldehyde (12.2 g, 0.1 mol) was used instead of 3,4-dihydroxybenzaldehyde (13.8 g, 0.1 mol). (Mw: 2,120)

[0153] [Chemical formula A]

[0154]

[0155] Synthesis Comparative Example 2

[0156] A polymer including a structural unit (repeating unit) represented by Chemical Formula B was synthesized according to the same method as Synthesis Example 1, except that pyrene (20.2 g, 0.1 mol) was used instead of 1-hydroxypyrene (21.8 g, 0.1 mol) and 4-hydroxybenzaldehyde (12.2 g, 0.1 mol) was used instead of 3,4-dihydroxybenzaldehyde (13.8 g, 0.1 mol). (Mw: 2,490)

[0157] [Chemical formula B]

[0158]

[0159] Synthesis Comparative Example 3

[0160] A polymer including a structural unit (repeating unit) represented by Chemical Formula C was synthesized according to the same method as Synthesis Example 1, except that pyrene (20.2 g, 0.1 mol) was used instead of 1-hydroxypyrene (21.8 g, 0.1 mol) and benzaldehyde (10.6 g, 0.1 mol) was used instead of 3,4-dihydroxybenzaldehyde (13.8 g, 0.1 mol). (Mw: 2,008)

[0161] [Chemical formula C]

[0162]

[0163] Comparative Synthesis Example 4

[0164] A polymer including a structural unit (repeating unit) represented by Chemical Formula D was synthesized according to the same method as Synthesis Example 1, except that 1-naphthol (14.4 g, 0.1 mol) was used instead of 1-hydroxypyrene (21.8 g, 0.1 mol) and benzaldehyde (10.6 g, 0.1 mol) was used instead of 3,4-dihydroxybenzaldehyde (13.8 g, 0.1 mol). (Mw: 2,011)

[0165] [Chemical formula D]

[0166]

[0167] Comparative Synthesis Example 5

[0168] A polymer including a structural unit (repeating unit) represented by Chemical Formula E was synthesized according to the same method as Synthesis Example 1 except that 4,4'-(9H-fluorene-9,9-diyl)diphenol (35.0 g, 0.1 mol) was used instead of 1-hydroxypyrene (21.8 g, 0.1 mol). (Mw: 2,472)

[0169] [Chemical formula E]

[0170]

[0171] Evaluation 1. Solubility evaluation

[0172] Weigh 5.0 grams of polymers according to Synthesis Example 1 to Synthesis Example 4 and Synthesis Comparative Example 1 to Synthesis Comparative Example 5 respectively, dissolve them uniformly in 45 grams of PGMEA to prepare a 10 wt % solution, and then, filter with a 0.1 micron TEFLON (tetrafluoroethylene) filter. The filtered samples are subdivided and weighed by using an Al dish, respectively, and the mass of the Al dish is known to measure the initial mass of the solution. Subsequently, the solvent in the Al dish is dried for 20 minutes in an oven at 160°C, and the mass is measured again.

[0173] According to the mass difference before and after drying, each solid content of the solution was calculated according to calculation equation 1.

[0174] [Calculation equation 1]

[0175] Solid content (%) = (mass after drying at 160°C for 20 minutes / initial mass of solution) × 100

[0176] (Table 1)

[0177] Solubility in PGMEA Synthesis Example 1 O Synthesis Example 2 O Synthesis Example 3 O Synthesis Example 4 O Synthesis Comparative Example 1 △ Synthesis Comparative Example 2 X Synthesis Comparative Example 3 X Comparative Synthesis Example 4 O Comparative Synthesis Example 5 O

[0178] O: Solid content greater than or equal to 9%

[0179] △: Solid content greater than or equal to 8% and less than 9%

[0180] X: Solid content less than 8%

[0181] Referring to Table 1, compared with the polymers according to Comparative Synthesis Examples 1 to 5, the polymers according to Synthesis Examples 1 to 4 exhibited improved or equal solubility.

[0182] Formation of hard mask composition

[0183] 1.2 grams of the polymers according to Synthesis Examples 1 to 4 and Comparative Examples 1 to 5 were obtained respectively, and then uniformly dissolved in 18 grams of PGMEA, and filtered with 0.1 micron TEFLON (tetrafluoroethylene) to prepare hard mask compositions according to Examples 1 to 4 and Comparative Examples 1 to 5.

[0184] Evaluation 2: Evaluation of etching resistance

[0185] The hard mask compositions according to Examples 1 to 4 and Comparative Examples 1 to 5 were respectively coated on a silicon wafer and heat-treated on a hot plate at about 400° C. for 2 minutes to form an organic film.

[0186] The thickness of the organic film was measured by using a ST5000 thin film thickness meter manufactured by K-MAC, and then, by using N 2 / O 2 Mixed gas (50mT / 300W / 10O 2 / 50N 2 ) After dry etching for one minute, the thickness of the organic film was measured again.

[0187] The difference in thickness of the organic film before and after dry etching and etching time are used to calculate a bulk etch rate (BER) according to calculation equation 2.

[0188] [Calculation equation 2]

[0189] Etching rate (angstroms / second) = (initial organic film thickness - organic film thickness after etching) / etching time

[0190] The results are shown in Table 2.

[0191] (Table 2)

[0192] Bulk etch rate (angstroms / second) Example 1 22.21 Example 2 22.35 Example 3 21.67 Example 4 22.72 Comparative Example 1 23.05 Comparative Example 2 24.25 Comparative Example 3 27.60 Comparative Example 4 28.53 Comparative Example 5 27.21

[0193] Referring to Table 2, compared with the organic films formed according to the hard mask compositions of Comparative Examples 1 to 5, the organic films formed according to the hard mask compositions of Examples 1 to 4 exhibited sufficient etching resistance against etching gas and thus improved etching resistance.

[0194] 3. Assessment of membrane density

[0195] The hard mask compositions according to Examples 1 to 4 and Comparative Examples 1 to 5 were spin-coated on silicon wafers, respectively, and then heat-treated on a hot plate at about 400° C. for about 2 minutes to form an organic film of about 1,000 angstroms.

[0196] The film density of the organic film was measured by an X-ray diffraction apparatus (Malvern PANalytical Ltd.).

[0197] The results are shown in Table 3.

[0198] (Table 3)

[0199] Film density (g / cm3) Example 1 1.44 Example 2 1.43 Example 3 1.45 Example 4 1.42 Comparative Example 1 1.38 Comparative Example 2 1.36 Comparative Example 3 1.33 Comparative Example 4 1.32 Comparative Example 5 1.28

[0200] Referring to Table 3, the organic films formed according to the hard mask compositions of Examples 1 to 4 exhibited improved film density compared to the organic films formed according to the hard mask compositions of Comparative Examples 1 to 5.

[0201] While the invention has been described in conjunction with what are presently considered to be practical example embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.

Claims

1. A hard mask composition comprising: A polymer comprising a structural unit represented by Chemical Formula 1, and Solvents, wherein the polymer has a weight average molecular weight of 1,500 to 100,000, and an amount of the polymer is in a range of 1 wt % to 30 wt % based on the total amount of the hardmask composition: [Chemical formula 1] Wherein, in Chemical Formula 1, A is a substituted or unsubstituted pyrene group, B is hydrogen, deuterium, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, halogen, nitro, amino, hydroxyl, or a combination thereof, R 1 to R 5 are independently hydrogen, deuterium, hydroxyl, substituted or unsubstituted C1 to C30 alkoxy, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C2 to C30 alkenyl, substituted or unsubstituted C2 to C30 alkynyl, substituted or unsubstituted C1 to C30 heteroalkyl, substituted or unsubstituted C3 to C30 cycloalkyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C3 to C30 heterocyclyl, or a combination thereof, and R 1 to R 5 At least two of the groups are independently hydroxy, substituted or unsubstituted C1 to C30 alkoxy, or a combination thereof.

2. The hard mask composition according to claim 1, wherein A is unsubstituted pyrene, or a pyrene group substituted with at least one substituent, wherein the substituents are independently deuterium, hydroxyl, substituted or unsubstituted C1 to C30 alkoxy, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C2 to C30 alkenyl, substituted or unsubstituted C2 to C30 alkynyl, substituted or unsubstituted C1 to C30 heteroalkyl, substituted or unsubstituted C3 to C30 cycloalkyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C3 to C30 heterocyclyl, or a combination thereof. 3 . The hardmask composition according to claim 1 , wherein A is an unsubstituted pyrene group or a pyrene group substituted with at least one hydroxyl group.

4. The hard mask composition according to claim 1, wherein R 1 to R 5 Two or three of the groups are independently hydroxy, substituted or unsubstituted methoxy, substituted or unsubstituted ethoxy, substituted or unsubstituted propoxy, substituted or unsubstituted butoxy, or a combination thereof.

5. The hard mask composition according to claim 1, wherein R 3 and R 4 are independently hydroxy, substituted or unsubstituted methoxy, substituted or unsubstituted ethoxy, substituted or unsubstituted propoxy, substituted or unsubstituted butoxy, or a combination thereof; R 3 and R 5 are independently hydroxy, substituted or unsubstituted methoxy, substituted or unsubstituted ethoxy, substituted or unsubstituted propoxy, substituted or unsubstituted butoxy, or a combination thereof; or R 1 , R 3 and R 5 are independently hydroxy, substituted or unsubstituted methoxy, substituted or unsubstituted ethoxy, substituted or unsubstituted propoxy, substituted or unsubstituted butoxy, or a combination thereof.

6. The hard mask composition according to claim 1, wherein the structural unit represented by Chemical Formula 1 is represented by one of Chemical Formula 2 to Chemical Formula 4: [Chemical formula 2] [Chemical formula 3] [Chemical formula 4] in, In Chemical Formula 2 to Chemical Formula 4, B is hydrogen, deuterium, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, halogen, nitro, amino, hydroxyl, or a combination thereof, R 1 , R 3 , R 4 and R 5 are independently hydroxy, substituted or unsubstituted methoxy, substituted or unsubstituted ethoxy, substituted or unsubstituted propoxy, substituted or unsubstituted butoxy, or a combination thereof, and R 6 is hydrogen, hydroxy, substituted or unsubstituted methoxy, substituted or unsubstituted ethoxy, substituted or unsubstituted propoxy, substituted or unsubstituted butoxy, or a combination thereof.

7. The hard mask composition according to claim 1, wherein The structural unit represented by Chemical Formula 1 is derived from the following reaction mixture, the reaction mixture comprising: Substituted or unsubstituted pyrene, and benzaldehyde substituted with at least two substituents, The substituents may independently be hydroxyl, substituted or unsubstituted C1 to C30 alkoxy, or a combination thereof. 8 . The hardmask composition according to claim 7 , wherein the substituted or unsubstituted pyrene is pyrene or hydroxypyrene. 9 . The hardmask composition of claim 7 , wherein the benzaldehyde substituted with at least two substituents is dihydroxybenzaldehyde, hydroxymethoxybenzaldehyde, hydroxyethoxybenzaldehyde, hydroxypropoxybenzaldehyde, hydroxybutoxybenzaldehyde, trihydroxybenzaldehyde, or a combination thereof.

10. A hard mask layer comprising a cured product of the hard mask composition according to any one of claims 1 to 9.

11. A method for forming a pattern, comprising: coating the hard mask composition as claimed in any one of claims 1 to 9 on the material layer and heat-treating the resultant to form a hard mask layer, forming a photoresist layer on the hard mask layer, exposing and developing the photoresist layer to form a photoresist pattern, selectively removing the hard mask layer using the photoresist pattern to expose a portion of the material layer, and The exposed portion of the material layer is etched.

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